CN109929113B - Silicone oligomer for bonding lithium battery electrode and preparation method thereof - Google Patents
Silicone oligomer for bonding lithium battery electrode and preparation method thereof Download PDFInfo
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- CN109929113B CN109929113B CN201910089229.XA CN201910089229A CN109929113B CN 109929113 B CN109929113 B CN 109929113B CN 201910089229 A CN201910089229 A CN 201910089229A CN 109929113 B CN109929113 B CN 109929113B
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- Prior art keywords
- silane
- lactate
- ethyl
- lithium battery
- bonding
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 70
- 229920001296 polysiloxane Polymers 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title abstract description 13
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910000077 silane Inorganic materials 0.000 claims abstract description 67
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 230000003068 static effect Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 100
- -1 alkyl alkoxy silane Chemical compound 0.000 claims description 69
- 238000009833 condensation Methods 0.000 claims description 46
- 230000005494 condensation Effects 0.000 claims description 46
- 230000007062 hydrolysis Effects 0.000 claims description 46
- 238000006460 hydrolysis reaction Methods 0.000 claims description 46
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 41
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 38
- 125000003545 alkoxy group Chemical group 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 238000010992 reflux Methods 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 229940116333 ethyl lactate Drugs 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000003085 diluting agent Substances 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 5
- YNSTXWACVFMCBI-UHFFFAOYSA-N [SiH4].C(C(O)C)(=O)O Chemical compound [SiH4].C(C(O)C)(=O)O YNSTXWACVFMCBI-UHFFFAOYSA-N 0.000 claims description 5
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229940057867 methyl lactate Drugs 0.000 claims description 4
- MLXDKRSDUJLNAB-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F MLXDKRSDUJLNAB-UHFFFAOYSA-N 0.000 claims description 4
- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- WQVJKRKRRMJKMC-UHFFFAOYSA-N diethoxy-methyl-octylsilane Chemical compound CCCCCCCC[Si](C)(OCC)OCC WQVJKRKRRMJKMC-UHFFFAOYSA-N 0.000 claims description 3
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 claims description 3
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 claims description 3
- GOIPELYWYGMEFQ-UHFFFAOYSA-N dimethoxy-methyl-octylsilane Chemical compound CCCCCCCC[Si](C)(OC)OC GOIPELYWYGMEFQ-UHFFFAOYSA-N 0.000 claims description 3
- XKRPWHZLROBLDI-UHFFFAOYSA-N dimethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OC)OC XKRPWHZLROBLDI-UHFFFAOYSA-N 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 3
- MCTWTUQSOKLGFJ-UHFFFAOYSA-N hexadecyl-dimethoxy-methylsilane Chemical compound CCCCCCCCCCCCCCCC[Si](C)(OC)OC MCTWTUQSOKLGFJ-UHFFFAOYSA-N 0.000 claims description 3
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical group CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 3
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 3
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- LGRXVPPCSQDLGU-UHFFFAOYSA-N 2-hydroxy-1-silylpropan-1-one Chemical compound C(C(O)C)(=O)[SiH3] LGRXVPPCSQDLGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- MHNUEQUGTGMGFX-UHFFFAOYSA-N diethoxy-hexadecyl-methylsilane Chemical compound CCCCCCCCCCCCCCCC[Si](C)(OCC)OCC MHNUEQUGTGMGFX-UHFFFAOYSA-N 0.000 claims description 2
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 2
- AILBOMWJRYLVFG-UHFFFAOYSA-N dodecyl-diethoxy-methylsilane Chemical compound CCCCCCCCCCCC[Si](C)(OCC)OCC AILBOMWJRYLVFG-UHFFFAOYSA-N 0.000 claims description 2
- PELGKMTVNFFDDL-UHFFFAOYSA-N dodecyl-dimethoxy-methylsilane Chemical compound CCCCCCCCCCCC[Si](C)(OC)OC PELGKMTVNFFDDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 41
- 235000019441 ethanol Nutrition 0.000 description 28
- 238000005160 1H NMR spectroscopy Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 21
- 230000001105 regulatory effect Effects 0.000 description 21
- 239000011949 solid catalyst Substances 0.000 description 21
- 238000005303 weighing Methods 0.000 description 21
- 230000010354 integration Effects 0.000 description 20
- NAGUZDIKIVJVAO-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecan-2-yloxy-(1,1,2,2,2-pentafluoroethoxy)-(1,1,2,2,2-pentafluoroethyl)-(trifluoromethyl)silane Chemical compound FC(F)(F)C(F)(F)O[Si](C(F)(F)C(F)(F)F)(C(F)(F)F)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F NAGUZDIKIVJVAO-UHFFFAOYSA-N 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
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- 238000004458 analytical method Methods 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- NMUBRRLYMADSGF-UHFFFAOYSA-N 3-triethoxysilylpropan-1-ol Chemical compound CCO[Si](OCC)(OCC)CCCO NMUBRRLYMADSGF-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000003903 lactic acid esters Chemical class 0.000 description 3
- YTIMCGHFKPXWIV-UHFFFAOYSA-N 2-[dimethoxy(methyl)silyl]ethanol Chemical compound CO[Si](C)(OC)CCO YTIMCGHFKPXWIV-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- ZHTLMPWATZQGAP-UHFFFAOYSA-N 2-triethoxysilylethanol Chemical compound CCO[Si](CCO)(OCC)OCC ZHTLMPWATZQGAP-UHFFFAOYSA-N 0.000 description 2
- XKPFLKWPESVZJF-UHFFFAOYSA-N 3,3,3-trifluoropropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCC(F)(F)F XKPFLKWPESVZJF-UHFFFAOYSA-N 0.000 description 2
- ZMWJQGOYIBHQJG-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-ol Chemical compound CCO[Si](C)(OCC)CCCO ZMWJQGOYIBHQJG-UHFFFAOYSA-N 0.000 description 2
- LMVLVUPTDRWATB-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-ol Chemical compound CO[Si](C)(OC)CCCO LMVLVUPTDRWATB-UHFFFAOYSA-N 0.000 description 2
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 2
- SBCIVMFCVBDNOF-UHFFFAOYSA-N 4-triethoxysilylbutan-1-ol Chemical compound CCO[Si](OCC)(OCC)CCCCO SBCIVMFCVBDNOF-UHFFFAOYSA-N 0.000 description 2
- ALJGWNGJUARELQ-UHFFFAOYSA-N 6-triethoxysilylhexan-1-ol Chemical compound CCO[Si](OCC)(OCC)CCCCCCO ALJGWNGJUARELQ-UHFFFAOYSA-N 0.000 description 2
- HIKPIPSOMGMRPC-UHFFFAOYSA-N [dimethoxy(methyl)silyl]methanol Chemical compound CO[Si](C)(CO)OC HIKPIPSOMGMRPC-UHFFFAOYSA-N 0.000 description 2
- 230000022131 cell cycle Effects 0.000 description 2
- NZYLTTOTIRRHQA-UHFFFAOYSA-N decyl-diethoxy-methylsilane Chemical compound CCCCCCCCCC[Si](C)(OCC)OCC NZYLTTOTIRRHQA-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- HPEPIADELDNCED-UHFFFAOYSA-N triethoxysilylmethanol Chemical compound CCO[Si](CO)(OCC)OCC HPEPIADELDNCED-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- PLZKBKDFCKEXSU-UHFFFAOYSA-N 2-[diethoxy(methyl)silyl]ethanol Chemical compound OCC[Si](OCC)(OCC)C PLZKBKDFCKEXSU-UHFFFAOYSA-N 0.000 description 1
- BOSZBTFBHSYELP-UHFFFAOYSA-N 2-trimethoxysilylethanol Chemical compound CO[Si](OC)(OC)CCO BOSZBTFBHSYELP-UHFFFAOYSA-N 0.000 description 1
- UAIUVVKGOUWVST-UHFFFAOYSA-N 4-[diethoxy(methyl)silyl]butan-1-ol Chemical compound CCO[Si](C)(OCC)CCCCO UAIUVVKGOUWVST-UHFFFAOYSA-N 0.000 description 1
- PIDYPPNNYNADRY-UHFFFAOYSA-N 4-trimethoxysilylbutan-1-ol Chemical compound CO[Si](OC)(OC)CCCCO PIDYPPNNYNADRY-UHFFFAOYSA-N 0.000 description 1
- IMMPPGDSUREZKL-UHFFFAOYSA-N 6-trimethoxysilylhexan-1-ol Chemical compound CO[Si](OC)(OC)CCCCCCO IMMPPGDSUREZKL-UHFFFAOYSA-N 0.000 description 1
- AULPLRPIUNCZBS-UHFFFAOYSA-N CN=C=O.CCO[SiH](C)OCC Chemical compound CN=C=O.CCO[SiH](C)OCC AULPLRPIUNCZBS-UHFFFAOYSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
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- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
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- MISQRWJCJZSTQT-UHFFFAOYSA-N [SiH4].C(C(O)C)(=O)OCC Chemical compound [SiH4].C(C(O)C)(=O)OCC MISQRWJCJZSTQT-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- RPDMQUQDEIOJGO-UHFFFAOYSA-N [diethoxy(methyl)silyl]methanol Chemical compound CCO[Si](C)(CO)OCC RPDMQUQDEIOJGO-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
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- 125000005055 alkyl alkoxy group Chemical group 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- FIVJMCNNMIGYRO-UHFFFAOYSA-N bis(2-hydroxyethyl)-dimethylazanium Chemical compound OCC[N+](C)(C)CCO FIVJMCNNMIGYRO-UHFFFAOYSA-N 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
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- GWUJPMKBSYJFCK-UHFFFAOYSA-N decyl-dimethoxy-methylsilane Chemical compound CCCCCCCCCC[Si](C)(OC)OC GWUJPMKBSYJFCK-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- SPHALHRGAQVBKI-UHFFFAOYSA-N trimethoxysilylmethanol Chemical compound CO[Si](CO)(OC)OC SPHALHRGAQVBKI-UHFFFAOYSA-N 0.000 description 1
- FVCJARXRCUNQQS-UHFFFAOYSA-N trimethylsilyl dihydrogen phosphate Chemical compound C[Si](C)(C)OP(O)(O)=O FVCJARXRCUNQQS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Silicon Polymers (AREA)
Abstract
The invention discloses a siloxane oligomer for bonding lithium battery electrodes and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, adopting a solvent method to carry out molecular-level compatibility on silane, a catalyst and a solvent; then, a tubular static mixer is used for uniformly carrying out quantitative reaction when the siloxane is contacted with water, and the siloxane oligomer with narrow molecular weight distribution is prepared. The preparation method of the siloxane oligomer for bonding the lithium battery electrode is simple, low in cost, environment-friendly and convenient for industrialization. The prepared siloxane oligomer for bonding the lithium battery electrode can improve the high compatibility, high and low temperature resistance, stable charge and discharge efficiency and cohesiveness of the lithium battery.
Description
Technical Field
The invention relates to the field of lithium battery materials, in particular to an environment-friendly siloxane oligomer for bonding lithium battery electrodes and a preparation method thereof.
Background
With the rapid development of new energy electric vehicles, the lithium battery is used as the heart of the electric vehicle, and the performance improvement of the related electrolyte, anode and cathode materials, electrode bonding materials and the like is a hotspot and difficulty of research so far. Siloxane oligomers, which have fewer alkoxy groups in their structure and high crosslinking functionality, impart low VOC and high crosslinking efficiency, are widely used as modified polymeric materials.
The lithium battery electrode binding material is generally made of polymer materials such as polyacrylic acid (PPA), Styrene Butadiene Rubber (SBR), polyvinylidene fluoride (PVDF), and the like. However, since the PPA and SBR structures contain hydrophilic carboxyl groups or nonionic groups, the battery consumes a large amount of lithium ions during initial charge and discharge, thereby causing a large irreversible capacity loss; meanwhile, the thermal stability of the carboxyl group or the nonionic group is poor, and irreversible decarboxylation or low molecular ether bond cleavage reaction can occur in a higher temperature range, so that the high-temperature cycle and the storage property of the battery are greatly reduced, and the problems of high-temperature gas expansion and the like of the battery are caused. On the other hand, PVDF as a positive electrode material has the defects of chemical instability and poor compatibility, and has poor electrochemical cycling behavior in a silicon-containing electrode, so that the development of an electrolytic adhesive with high compatibility, high and low temperature resistance, stable charge and discharge efficiency and environmental protection is urgent.
US20080187838a1 describes a method of neutralizing the carboxyl groups in PPA with lithium hydroxide to reduce the irreversible capacity loss during the first charge and discharge of a lithium battery. However, the lithium salt generated by neutralization has high hydrophilicity, so that the pole piece is difficult to completely dry and the battery cyclicity is greatly damaged. Patent EP2432056a1 describes a polyvinyl alcohol modified PPA as a binder of a lithium ion battery negative electrode material, however, the binder has a weak lithium ion conducting capability, and when the amount of the binder is large, the internal resistance is sharply increased, and further technical problems such as reduction of charge-discharge efficiency and rate are caused.
The invention patent with patent number 201711115995.6 describes an SBR type binder, which is widely used for binding a negative electrode material system because of small addition amount of SBR and strong binding force between the SBR and an active substance and a current collector, but the SBR has the particle size range of 50-300 nm, is easy to repeatedly expand on a negative electrode to cause the SBR to be separated from the system, damages the integrity of a conductive system and greatly reduces the cycle performance.
US5776637 describes a PVDF binder with good irreversible adhesion to the electrode material particles, which ensures that the electrode can withstand large volume expansion and contraction during charge and discharge cycles without damaging the internal interconnectivity of the electrode, and allows smooth crossover of electrons. However, these binders based on organic solvents have many defects, PVDF binders need to be dissolved by a large amount of NMP solvent, and when PVDF with a concentration of 10-20% is used, the slurry shows an abnormal high viscosity behavior, which makes the electrode composition difficult to prepare, and meanwhile, NMP is used as the solvent, on one hand, the solvent is difficult to volatilize, time-consuming and complex in process; on the other hand, organic solvents are toxic and flammable, causing environmental pollution and safety problems.
US20120153219 describes a polyether modified siloxane binder, which overcomes the above-mentioned deficiencies of molecular structure in the adhesion of polar and non-polar lithium battery electrodes, not only endows the lithium ion with good lithium ion migration ability, but also has good adhesion stability between electrodes, but the method adopts a hydrosilylation method, and if a heat vulcanization method is not adopted, the vulcanization completely requires more than 72 hours, which limits the basis of wide application.
In view of the above, there is an urgent need to design a lithium battery electrode binding material that can overcome the defects of use under harsh conditions.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the environment-friendly siloxane oligomer for bonding the lithium battery electrode, which can improve the high compatibility, high and low temperature resistance, stable charge and discharge efficiency and adhesion of the lithium battery and is environment-friendly, and the preparation method thereof.
In order to achieve the above object, the inventors provide a silicone oligomer for lithium battery electrode bonding, which has the structure shown in formula I:
in the above formula, R1、R2Each indicates a carbon chain number of C3～C8With perfluoroalkyl ethyl or carbon chain number C1～C4An alkoxy group of (a); r3、R4Each represents a carbon number of C3～C16Saturated or unsaturated alkyl, cycloalkyl, aryl or carbon chains C1～C4An alkoxy group; r5、R6Respectively represents methyl, ethyl, vinyl, isopropyl or propyl, and has carbon number of C1～C4Alkoxy groups, methyl lactate, ethyl lactate, propyl lactate, or butyl lactate;q is hydroxymethylene, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl or C1～C4An alkoxy group; a. b and c are positive integers of 1-10.
The invention adopts the molecular structure of the siloxane oligomer for bonding the lithium battery electrode, solves the technical difficulty of structural defects of the traditional lithium battery electrode adhesive, and has the core advantages that: firstly, a reasonable polar group is designed in a molecular structure, so that the initial charge-discharge cycle life of the material is prolonged, and better charge-discharge efficiency and multiplying power are obtained; secondly, a lower nonpolar group is introduced into the molecular structure, so that the molecular structure is endowed with chemical medium resistance and compatibility; thirdly, enough active reaction groups are constructed in the molecular structure, so that the adhesive and the electrode are endowed with stable and long-acting cohesiveness. The carboxyl or ether group has excellent polar effect, and endows the lithium battery with good ion mobility and charge-discharge efficiency; and fourthly, the siloxane has lower surface energy and low polarity, and the lithium battery is endowed with good chemical stability and cohesiveness.
Preferably, the values of a, b and c in formula I satisfy the condition: 5 < a + b + c < 20 to satisfy compatibility of the lactate based siloxane oligomer with a matrix resin and a suitable degree of crosslinking.
The invention also provides a preparation method of the siloxane oligomer for bonding the lithium battery electrode, which comprises the following steps:
1) sequentially adding alkyl alkoxy silane and fluoro alkyl alkoxy silane and hydroxyalkyl silane and/or lactate silane into a dosage mixer, adding a diluent which does not react with siloxane and a supported catalyst, and continuously and uniformly stirring at room temperature to obtain a silane mixed solution;
2) adding a diluent which does not react with siloxane into metered water to obtain a diluent of water, dropwise adding the silane mixed solution obtained in the step 1) and the diluent of the water into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing, and after dropwise adding, adding the mixture into a second reactor to obtain a primary hydrolyzed/condensed siloxane oligomer; the mass ratio of the siloxane-unreactive diluent added into the water to the water is 5-10: 1; the molar weight of the added water is the same as the molar equivalent of alkoxy in the silane mixed solution;
3) and heating the second reactor to 40-80 ℃ for further hydrolysis/condensation reflux reaction, filtering out the solid supported catalyst when the equivalent hydrolysis/condensation between the alkoxy and water is finished, and removing the diluent to obtain the lactate-based siloxane oligomer for bonding the lithium battery electrode.
The preparation method has the advantages that: firstly, the compatibility of molecular level between silane and catalyst in the reaction process can be realized by adopting a solvent method; secondly, the tubular static mixer is designed and used, so that the siloxane can be uniformly quantitatively reacted when being contacted with water, siloxane oligomer with narrow molecular weight distribution can be obtained, and the defect of one-pot reaction is avoided.
Preferably, the alkylalkoxy silane, fluoro alkylalkoxy silane or lactate silane has a formula shown in formula II:
Rn-Si(OR7)(4-n)formula II;
when the formula of formula II represents an alkylalkoxysilane, R is a carbon chain number C3～C16Saturated or unsaturated alkyl, cycloalkyl or aryl; r7Is C1～C4An alkyl group; n is an integer of 1 or 2; more preferably, the alkylalkoxysilane is octyltriethoxysilane, propyltriethoxysilane, hexadecyltrimethoxysilane, dodecyltriethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, methylphenyldiethoxysilane, methyloctyldimethoxysilane, methyloctyldiethoxysilane, methyldecyldiethoxysilane, methyldecyldimethoxysilane, methyldecyldiethoxysilane, methylhexadecyldimethoxysilane, and the like, and such silicones have low polarity to impart compatibility to the lithium battery;
when formula II represents a fluoroalkylalkoxysilane, R is C3～C8Perfluoroalkyl ethyl, perfluoroalkyl methyl, perfluoroalkyl ethyl, perfluoroalkyl vinyl, perfluoroalkylRadical isopropyl or perfluoroalkylpropyl, R7Is C1～C4Alkyl, n is an integer of 1 or 2; more preferably, the fluoroalkyl alkoxy silane is methyl perfluorooctyl ethyl dimethoxy silane, methyl perfluorooctyl ethyl diethoxy silane, perfluorooctyl ethyl trimethoxy silane, perfluorooctyl ethyl triethoxy silane, methyl perfluorotridecyl ethyl dimethoxy silane, methyl perfluorotridecyl ethyl diethoxy silane, perfluorotridecyl ethyl trimethoxy silane, perfluorotridecyl ethyl triethoxy silane and the like, and the siloxane molecular structure has very low polarity and endows the lithium battery with chemical medium resistance;
when the formula of formula II represents lactylsilane, R is carbon chain number C3～C16Saturated or unsaturated alkyl, cycloalkyl or aryl; r7Is methyl lactate, ethyl lactate, propyl lactate or butyl lactate; n is an integer of 1 or 2. More preferably, the lactate polar siloxane is vinylmethyl trilactate silane, vinylpropyl trilactate silane, vinylbutyl trilactate silane, vinylethyl trilactate silane, methyl ethyl trilactate silane, vinylethyl trilactate silane, methyl vinyl ethyl dilactate silane, dimethyl ethyl dilactate silane and the like, and the molecular structure of the siloxane has higher polarity, so that the siloxane has better charge-discharge efficiency and multiplying power.
Preferably, the non-siloxane reactive diluent is one or a mixture of two or more of the following: methanol, ethanol, isopropanol, propanol, tetrahydrofuran, acetone, butanone, ethyl acetate or butyl acetate. More preferably, the non-siloxane reactive diluent is methanol, ethanol or butanone. The invention adopts the diluent to realize mild polymerization of siloxane in the hydrolysis/condensation copolymerization process, and avoids the defect that bulk polymerization is easy to implode or hydrolysis/condensation is not uniform.
Preferably, the carrier used in the supported catalyst is one or a mixture of two or more of the following: clay, styrene type spherical exchange resin, porous silica gel, precipitated or fumed silica, porous alumina, aluminum silicate, or porous ceramic. More preferably, the carrier used in the supported catalyst is styrene type spherical exchange resin or porous carrier silica gel.
Preferably, the catalyst is an acid type catalyst, and the acid catalyst is one of the following: titanate type, sulfuric acid type, phosphoric acid type, or sulfonic acid group type. More preferably, the catalyst is tetratrimethyl silicon titanate, dodecyl benzene sulfonic acid, trimethyl silicon based phosphoric acid or trifluoropropyl sulfonic acid. The catalyst can solve the problem that siloxane monomers obtain an oligomer structure with narrow molecular weight distribution in the hydrolysis/condensation process, and overcomes the technical defect that the siloxane hydrolysis/condensation or ring opening is easy to form the oligomer structure with high molecular weight in the alkali catalysis process. In addition, the catalyst is compounded by using an inorganic carrier, so that the technical problem that the liquid catalyst needs to be neutralized is solved.
Preferably, the molecular formula of the hydroxyalkane silane is shown as formula III:
in the formula III, W is hydroxymethylene, hydroxyethyl, hydroxypropyl, hydroxybutyl or hydroxyhexyl; z is methyl, ethyl, vinyl, isopropyl or propyl; r8Is C1～C3Saturated alkyl groups of (a); d is an integer of 0, 1 or 2. More preferably, the hydroxyalkyl siloxane is preferably methyl hydroxymethyl dimethoxy silane, methyl hydroxymethyl diethoxy silane, hydroxymethyl trimethoxy silane, hydroxymethyl triethoxy silane, methyl hydroxyethyl dimethoxy silane, methyl hydroxyethyl diethoxy silane, hydroxyethyl trimethoxy silane, hydroxyethyl triethoxy silane, methyl hydroxypropyl dimethoxy silane, methyl hydroxypropyl diethoxy silane, hydroxypropyl trimethoxy silane, hydroxypropyl triethoxy silane, methyl hydroxybutyl dimethoxy silane, methyl hydroxybutyl diethoxy silane, hydroxybutyl trimethoxy silane, hydroxybutyl triethoxy silane, methyl hydroxyhexyl dimethoxy silane, methyl hydroxyhexyl diethoxy silane, hydroxyhexyl trimethoxy silane, hydroxyhexyl triethoxy silane, and the like, which are imparted to lithium batteriesThe charge-discharge efficiency and rate are preferable, and particularly, methylhydroxypropyldimethoxysilane, methylhydroxypropyldiethoxysilane, hydroxypropyltrimethoxysilane or hydroxypropyltriethoxysilane is preferable. The hydroxyalkylsilane siloxane unit is designed in the molecular structure of the invention, so that the lithium battery has the first charge-discharge cycle life, and has good charge-discharge efficiency and rate, and good ion mobility and charge-discharge efficiency.
The invention has the beneficial effects that: the molecular structure design is adopted, the balance regulation and control of molecular polarity and non-polarity are carried out, the molecular structure of the prepared siloxane oligomer for bonding the lithium battery electrode contains polar group carboxyl or ether group, and the carboxyl or ether group has excellent polar effect, so that the lithium battery is endowed with the first charge-discharge circulation life, and the lithium battery obtains good ion mobility, charge-discharge efficiency and multiplying power; secondly, the molecular structure contains lower nonpolar group perfluoroalkyl ethyl and long-chain alkyl, so that the lithium battery is endowed with chemical medium resistance and compatibility; in addition, the siloxane oligomer for bonding the lithium battery electrode not only has higher molecular weight, but also has enough active reaction groups of PVDF and siloxane, so that the siloxane oligomer has lower surface energy and low polarity, and further the lithium battery adhesive and the electrode are endowed with stable and long-acting bonding property.
In a word, the preparation method of the siloxane oligomer for bonding the lithium battery electrode is simple, low in cost, environment-friendly and convenient for industrialization. The prepared siloxane oligomer for bonding the lithium battery electrode can improve the high compatibility, high and low temperature resistance, stable charge and discharge efficiency and cohesiveness of the lithium battery.
Detailed Description
To explain technical contents, structural features, objects and effects of the technical solutions in detail, the following detailed descriptions are given with reference to specific embodiments
Example 1
Firstly, 99.6 g (0.3mol) of dodecyl triethoxysilane, 61.0 g (0.1mol) of perfluorooctyl ethyl methyl diethoxysilane, 243.6 g (0.6mol) of vinyl ethyl trilactate silane, 500ml of anhydrous ethanol and silica gel supported tetratrimethyl silicon titanate catalyst are sequentially added into a dosage mixer, and the mixture is stirred continuously at room temperature for 30min to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 102ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared (the theoretical value/actual value of the lactate content is calculated to be 28.33%/28.30% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 9.07%/9.02%).
Example 2
Firstly, metered 44.5 g (0.3mol) of methylpropyldimethoxysilane, 61.0 g (0.1mol) of perfluorooctylethylmethyldiethoxysilane, 236.4 g (0.6mol) of methyltrihalolsilane, 500ml of methanol and a clay-supported tetratrimethylsilyltitanate catalyst are sequentially added into a dosage mixer, and the mixture is stirred for 30min at room temperature to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 102ml of methanol to uniformly mix, dropwise adding the uniformly mixed silane solution and methanol aqueous solution into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, methanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared, (the theoretical value/actual value of the lactate content is calculated to be 27.49%/27.43% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 9.09%/9.04%).
Example 3
Firstly, 99.6 g (0.3mol) of dodecyl triethoxysilane, 55.5 g (0.1mol) of methyl perfluorooctyl ethyl dimethoxysilane, 182.4 g (0.6mol) of methyl vinyl ethyl lactate silane, 500ml of anhydrous ethanol and silica gel supported tetratrimethyl silicon titanate catalyst are sequentially added into a dosage mixer, and are stirred for 30min at room temperature to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 102ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared, (the theoretical value/actual value of the lactate content is calculated to be 20.58%/20.52% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 12.11%/12.07%).
Example 4
Firstly, measured 53.0 g (0.3mol) of methylpropyldiethoxysilane, 61.0 g (0.1mol) of perfluorooctylethylmethyldiethoxysilane, 182.4 g (0.6mol) of dimethyldiethanolammonium silane, 500ml of butanone and styrene type spherical exchange resin supported tetratrimethylsilylium titanate are sequentially added into a dosage mixer, and the mixture is continuously stirred at room temperature for 30min to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 100ml of butanone for uniform mixing, dropwise adding the uniformly mixed silane solution and butanone aqueous solution at constant speed at room temperature into a tubular static reaction mixer, realizing quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, a supported solid catalyst is filtered out, butanone/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding lithium battery electrodes with the chain number of 10 is prepared, (the theoretical value/actual value of the lactate content is calculated to be 19.77%/19.72% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 12.52%/12.46%).
Example 5
Firstly, 99.6 g (0.3mol) of dodecyl triethoxysilane, 57.0 g (0.1mol) of perfluorooctyl ethyl trimethoxysilane, 222 g (0.6mol) of vinylmethyl trilactate silane, 500ml of anhydrous ethanol and silica gel supported tetratrimethylsilylitate catalyst are sequentially added into a dosage mixer, and the mixture is stirred continuously at room temperature for 30min to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 100ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared, (the theoretical value/actual value of the lactate content is calculated to be 25.81%/25.77% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 9.95%/9.88%).
Example 6
Firstly, measured 55.0 g (0.3mol) of methylphenyldimethoxysilane, 61.0 g (0.1mol) of perfluorooctylethylmethyldiethoxysilane, 268.8 g (0.6mol) of vinyltrislactopropyl silane, 500ml of anhydrous ethanol and a silica gel-supported tetratrimethylsilyltitanate catalyst were sequentially added to a dosage mixer, and the mixture was stirred at room temperature for 30min to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 100ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared, (the theoretical value/actual value of the lactate content is calculated to be 28.48%/28.43% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 9.02%/8.98%).
Example 7
Firstly, 99.6 g (0.3mol) of dodecyl triethoxysilane, 61.0 g (0.1mol) of perfluorooctyl ethyl triethoxysilane, 294 g (0.6mol) of butyl vinyl trilactate silane, 500ml of isopropanol and silica gel supported tetratrimethyl silicon titanate catalyst are sequentially added into a dosage mixer, and the mixture is continuously stirred at room temperature for 30min to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 103ml of isopropanol to be uniformly mixed, dropwise adding the silane solution and the isopropanol water solution which are uniformly mixed into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, isopropanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared, (the theoretical value/actual value of the lactate content is calculated to be 31.15%/31.10% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 8.25%/8.21%).
Example 8
Firstly, 63.0 g (0.3mol) of methylphenyldiethoxysilane, 58.0 g (0.1mol) of perfluorooctylethylmethyldiethoxysilane, 243.6 g (0.6mol) of vinyltris (ethyl) lactate silane, 500ml of anhydrous ethanol and precipitated silica supported tetratrimethylsilyltitanate catalyst which are metered are sequentially added into a dosage mixer, and the mixture is continuously stirred at room temperature for 30min to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 160ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 5 is prepared (the theoretical value/actual value of the lactate content is calculated to be 28.80%/28.76% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 6.92%/6.88%).
Example 9
Firstly, 99.6 g (0.3mol) of dodecyl triethoxysilane, 80.0 g (0.1mol) of methyl perfluorotridecyl ethyl dimethoxysilane, 243.6 g (0.6mol) of ethyl vinyl trilactate silane, 500ml of anhydrous ethanol and fumed silica supported tetratrimethylsilyltitanate catalyst were sequentially added to a dosage mixer and stirred at room temperature for 30min to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 150ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 15 is prepared (the theoretical value/actual value of the lactate content is calculated by H-NMR area integration and is 25.53%/25.49%, and the theoretical value/actual value of the ethoxy content is 5.40%/5.36%).
Example 10
Firstly, 65.5 g (0.3mol) of methyloctyldimethoxysilane, 61.0 g (0.1mol) of perfluorooctylethylmethyldiethoxysilane, 243.6 g (0.6mol) of methylhydroxymethyldimethoxysilane, 500ml of anhydrous ethanol and a silica gel-supported tetratrimethylsilyltitanate catalyst were metered into a dosage mixer in this order and stirred at room temperature for 30min to disperse them uniformly; secondly, weighing 16.2 g (0.9mol) of deionized water and 102ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 20 is prepared (the theoretical value/actual value of the lactate content is calculated to be 25.09%/25.07% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 5.20%/5.16%).
Example 11
Firstly, 99.6 g (0.3mol) of dodecyl triethoxysilane, 83.0 g (0.1mol) of methyl perfluorotridecyl ethyl diethoxysilane, 133.2 g (0.6mol) of hydroxypropyl triethoxysilane, 500ml of propanol and a silica gel-supported tetratrimethylsilylium titanate catalyst are metered into a dosage mixer in sequence and stirred continuously at room temperature for 30min to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 103ml of propanol, uniformly mixing, dropwise adding the uniformly mixed silane solution and the water solution of the propanol into a tubular static reaction mixer at a constant speed at room temperature, and realizing quantitative, timed and uniform mixing reaction to obtain primary hydrolyzed/condensed siloxane oligomer; and finally, the primary hydrolyzed/condensed siloxane oligomer enters a second reactor with stirring, the temperature is increased and regulated to further perform hydrolysis/condensation reflux reaction within the range of 60 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, and the propanol is removed to prepare the hydroxyalkyl siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 (the theoretical value/actual value of the hydroxypropyl content calculated by H-NMR area integration is 15.80%/15.77%, and the theoretical value/actual value of the ethoxy content is 22.10%/22.06%).
Example 12
Firstly, 74 g (0.3mol) of methyl octyl diethoxysilane, 61.0 g (0.1mol) of perfluoro octyl ethyl methyl diethoxysilane, 133.2 g (0.6mol) of hydroxymethyl triethoxysilane, 500ml of absolute ethyl alcohol and porous alumina supported tetratrimethyl silicon titanate catalyst are added into a dosage mixer in sequence, and the mixture is stirred continuously at room temperature for 30min to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 205ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the primary hydrolyzed/condensed siloxane oligomer enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 50 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol is removed, and the hydroxyalkyl siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared (the theoretical value/actual value of hydroxypropyl content calculated by H-NMR area integration is 8.98%/8.94%, and the theoretical value/actual value of ethoxy content is 23.89%/23.86%).
Example 13
Firstly, 107 g (0.3mol) of methylhexadecyl diethoxysilane, 61.0 g (0.1mol) of perfluorooctyl ethyl methyldiethoxysilane, 133.2 g (0.6mol) of hydroxyethyl triethoxysilane, 500ml of tetrahydrofuran and a silica gel-supported tetratrimethylsilylitate catalyst were metered into a dosage mixer in this order and stirred continuously at room temperature for 30min to disperse them uniformly; secondly, weighing 16.2 g (0.9mol) of deionized water and 100ml of tetrahydrofuran, uniformly mixing, dropwise adding the uniformly mixed silane solution and tetrahydrofuran water solution at room temperature at a constant speed into a tubular static reaction mixer, and realizing quantitative, timed and uniform mixing reaction to obtain primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, tetrahydrofuran is removed, and the hydroxyalkyl siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared (the theoretical value/actual value of the hydroxypropyl content calculated by H-NMR area integration is 12.52%/12.54%, and the theoretical value/actual value of the ethoxy content is 22.96%/22.92%).
Example 14
Firstly, 82 g (0.3mol) of methyldodecyldimethoxysilane, 61.0 g (0.1mol) of perfluorooctylethylmethyldiethoxysilane, 133.2 g (0.6mol) of hydroxybutyltriethoxysilane, 500ml of acetone and a silica gel-supported tetratrimethylsilylium titanate catalyst were metered into a dosage mixer in this order and stirred continuously at room temperature for 30min to disperse them uniformly; secondly, weighing 16.2 g (0.9mol) of deionized water and 103ml of acetone to uniformly mix, dropwise adding the uniformly mixed silane solution and acetone aqueous solution into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the primary hydrolyzed/condensed siloxane oligomer enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, acetone is removed, and the hydroxyalkyl siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared (the theoretical value/actual value of hydroxypropyl content calculated by H-NMR area integral is 18.85%/18.80%, and the theoretical value/actual value of ethoxy content is 21.30%/21.26%).
Example 15
First, 99.6 g (0.3mol) of dodecyltriethoxysilane, 82.0 g (0.1mol) of perfluorotridecylethyltrimethoxysilane, 133.2 g (0.6mol) of hydroxyhexyltriethoxysilane, 500ml of anhydrous ethanol and an aluminum silicate supported tetratrimethylsilyltitanate catalyst were metered into a dosage mixer in this order and stirred continuously at room temperature for 30min to disperse them uniformly; secondly, weighing 16.2 g (0.9mol) of deionized water and 100ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the primary hydrolyzed/condensed siloxane oligomer enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol is removed, and the hydroxyalkyl siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared (the theoretical value/actual value of hydroxypropyl content calculated by H-NMR area integration is 24.34%/24.30%, and the theoretical value/actual value of ethoxy content is 19.88%/19.85%).
Example 16
First, 99.6 g (0.3mol) of octyltriethoxysilane, 86.0 g (0.1mol) of perfluorotridecylethyltriethoxysilane, 268.8 g (0.6mol) of vinyltrispropyl lactate silane, 500ml of ethyl acetate and a silica gel-supported tetratrimethylsilylitate catalyst were metered into a dosage mixer in this order and stirred continuously at room temperature for 30min to disperse them uniformly; secondly, weighing 16.2 g (0.9mol) of deionized water and 100ml of ethyl acetate to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the ethyl acetate water solution into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 60 ℃, when the quantitative reaction between alkoxy and water is finished, a supported solid catalyst is filtered out, ethyl acetate/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared, (the theoretical value/actual value of the lactate content is calculated to be 36.68%/36.65% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 7.20%/7.16%).
Example 17
Firstly, metered amounts of 61.8 g (0.3mol) of propyltriethoxysilane, 61.0 g (0.1mol) of perfluorooctylethylmethyldiethoxysilane, 268.8 g (0.6mol) of vinyltrislactopropyl silane, 500ml of anhydrous ethanol and a silica gel-supported trifluoropropylsulfonic acid catalyst were added in sequence to a dosage mixer, and stirring was continued at room temperature for 30min to disperse them uniformly; secondly, weighing 16.2 g (0.9mol) of deionized water and 100ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 40 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared, (the theoretical value/actual value of the lactate content is calculated to be 40.33%/40.30% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 7.92%/7.88%).
Example 18
Firstly, metered amounts of 104.0 g (0.3mol) of hexadecyltrimethoxysilane, 61.0 g (0.1mol) of perfluorooctylethyltriethoxysilane, 268.8 g (0.6mol) of vinyltrislactic propyl ester silane, 500ml of butyl acetate and a silica gel-supported tetratrimethylsilylium titanate catalyst were added in sequence to a dosage mixer, and stirred continuously at room temperature for 30min to disperse uniformly; secondly, weighing 16.2 g (0.9mol) of deionized water and 100ml of butyl acetate to be uniformly mixed, dropwise adding the uniformly mixed silane solution and butyl acetate water solution into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 80 ℃, when the quantitative reaction between alkoxy and water is finished, a supported solid catalyst is filtered out, butyl acetate/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for lithium battery electrode bonding with the chain number of 10 is prepared, (the theoretical value/actual value of the lactate content is calculated to be 39.80%/39.77% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 11.94%/11.90%).
Example 19
Firstly, 99.6 g (0.3mol) of methylhexadecyl dimethoxy silane, 61.0 g (0.1mol) of perfluorooctyl ethyl methyldiethoxysilane, 90.0 g (0.6mol) of methylhydroxyethyl dimethoxy silane, 500ml of anhydrous ethanol and a silica gel-supported dodecylbenzenesulfonic acid catalyst are metered into a dosage mixer in sequence, and the mixture is stirred continuously at room temperature for 30min to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 100ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared (the theoretical value/actual value of the lactate content is calculated to be 28.33%/28.30% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 9.07%/9.02%).
Example 20
Firstly, 99.6 g (0.3mol) of methyldodecyl diethoxy silane, 61.0 g (0.1mol) of perfluorooctyl ethyl methyldiethoxy silane, 243.6 g (0.6mol) of ethyl vinyl trilactate silane, 500ml of absolute ethyl alcohol and a porous ceramic supported trimethylsilyl phosphoric acid catalyst which are metered are sequentially added into a dosage mixer, and the mixture is continuously stirred at room temperature for 30min to be uniformly dispersed; secondly, weighing 16.2 g (0.9mol) of deionized water and 100ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared (the theoretical value/actual value of the lactate content is calculated to be 28.33%/28.30% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 9.07%/9.02%).
Example 21
Firstly, 66.3 g (0.2mol) of dodecyltriethoxysilane, 61.0 g (0.1mol) of perfluorooctylethylmethyldiethoxysilane, 243.6 g (0.6mol) of ethylvinyltrilactate silane, 17.80 g (0.1mol) of methylhydroxybutyldimethoxysilane, 500ml of anhydrous ethanol and a silica gel-supported tetratrimethylsilyltitanate catalyst were metered into a dosage mixer in this order and stirred at room temperature for 30min to disperse them uniformly; secondly, weighing 16.2 g (0.9mol) of deionized water and 102ml of absolute ethyl alcohol to be uniformly mixed, dropwise adding the uniformly mixed silane solution and the water solution of the ethyl alcohol into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing reaction, and obtaining primary hydrolyzed/condensed siloxane oligomer; and finally, the siloxane oligomer subjected to primary hydrolysis/condensation enters a second reactor with stirring, the temperature is increased and regulated to further carry out hydrolysis/condensation reflux reaction within the range of 70 ℃, when the quantitative reaction between alkoxy and water is finished, the supported solid catalyst is filtered out, ethanol/ethyl lactate is removed, and the biodegradable lactate type siloxane oligomer special for bonding the lithium battery electrode with the chain number of 10 is prepared (the theoretical value/actual value of the lactate content is calculated to be 28.33%/28.30% through H-NMR area integration, and the theoretical value/actual value of the ethoxy content is 9.07%/9.02%).
Example 22
The lactic acid ester oligosiloxane compound prepared in the above example 1 is used to crosslink polyether copolymer containing lactic acid ester oligosiloxane structural unit, and the specific preparation application examples are as follows:
(1) methyl isocyanate methyl diethoxy silane and polypropylene glycol (M)n12000), reacting at room temperature for 4 hours at the stirring speed of 200-300 rpm, and then heating to 70 ℃ to react to a stoichiometric point to prepare a polymer A; isophorone diisocyanate (IPDI), the siloxane oligomer prepared in example 1, and polypropylene glycol (M)n12000) and dibutyl tin dilaurate are evenly mixed at room temperature, and the temperature is increased to 70 ℃ to react to a stoichiometric point to prepare a polymer B;
(2) when the polyether copolymer is used, the polymer A and the polymer B are mixed according to the molar ratio of 1.5:1 for polymerization to obtain the polyether copolymer with the main chain containing structural units of lactate and/or hydroxyalkyl siloxane.
(3) Carbon composite material: conductive carbon: and uniformly mixing the alkoxy silane terminated polyether and the siloxane oligomer binder, stirring for 1h, coating the mixture on an aluminum foil, and drying in vacuum at 60 ℃ to obtain the positive pole piece.
Example 23 example 42
By using the preparation method of example 22 and sequentially replacing the siloxane oligomer prepared in example 1 in example 22 with the siloxane oligomers prepared in examples 2 to 21, block polyether copolymers of different oligosiloxane types were synthesized, respectively.
The coating performance indices of the polyether copolymers containing oligosiloxane structural units prepared according to examples 22 to 42 are shown in table 1.
Table 1 shows the preparation of polyether copolymers containing siloxane structural units obtained in examples 22 to 42
Coating inspection data
The test method for the performance test data of the bonded battery in table 1 is as follows:
(1) first charge-discharge efficiency: the ratio of discharge capacity to charge capacity of the first charge-discharge cycle is shown, and metal lithium is used as a negative electrode, LiNiMoCoO2As a positive electrode material, a Li/Celgard2500 diaphragm/LiNiMoCoO is assembled2The button cell is subjected to constant current analysis on a Xinwei cell cycle workstation system, the test voltage range is 2.5-4.25V, and the charge-discharge multiplying power is 0.5C.
(2) High-temperature cycle test: using metallic lithium as negative electrode, LiNiMoCoO2As a positive electrode material, a Li/Celgard2500 diaphragm/LiNiMoCoO is assembled2The button cell is subjected to constant current analysis on a Xinwei cell circulating workstation system, the test voltage range is 2.5-4.25V, the charge-discharge multiplying power is 0.5C, and the test temperature is 60 ℃.
(3) And (3) low-temperature cyclicity test: using metallic lithium as negative electrode, LiNiMoCoO2As a positive electrode material, a Li/Celgard2500 diaphragm/LiNiMoCoO is assembled2The button cell is subjected to constant current analysis on a Xinwei cell circulating workstation system, the test voltage range is 2.5-4.25V, the charge-discharge multiplying power is 0.5C, and the test temperature is 10 ℃.
(4) Capacity retention ratio: using metallic lithium as negative electrode, LiNiMoCoO2As a positive electrode material, a Li/Celgard2500 diaphragm/LiNiMoCoO is assembled2The button cell is subjected to constant current analysis on a Xinwei cell cycle workstation system, the test voltage range is 2.5-4.25V, the charge-discharge multiplying power is 0.5C, and the cycle lasts 150 weeks.
(5) And (3) testing alternating current impedance: using metallic lithium as negative electrode, LiNiMoCoO2As a positive electrode material, a Li/Celgard2500 diaphragm/LiNiMoCoO is assembled2The button cell was analyzed on an electrochemical workstation at a frequency of 100kHz-10mHz and a perturbation voltage of 5 mV.
As can be seen from table 1, the adhesive of the polyether copolymer containing an oligosiloxane structural unit of the present invention exhibits excellent first charge-discharge efficiency, high temperature cyclability, low temperature cyclability, stable capacity retention rate, ac resistance, etc., and particularly, the adhesive exhibits excellent electrical cyclability as the number of chain alkyl siloxane groups increases and the structural units of hydroxymethyl siloxane units and fluorosilicone units increase.
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein or by using equivalent structures or equivalent processes performed in the present specification, and are included in the scope of the present invention.
Claims (8)
1. A silicone oligomer for bonding an electrode of a lithium battery, characterized in that: the structure is shown as formula I:
in the above formula, R1、R2Each indicates a carbon chain number of C3～C8Or R is perfluoroalkyl ethyl, or1、R2Wherein any one of the groups is a carbon chain having the number C3～C8And the other group is a carbon chain number C1～C4An alkoxy group of (a); r3、R4Wherein any one group is C3～C16A saturated or unsaturated alkyl or cycloalkyl radical, the other radical having a carbon number of C3～C16Saturated or unsaturated alkyl, cycloalkyl, aryl or carbon chains C1～C4An alkoxy group;
R5、R6wherein any one group is methyl lactate, ethyl lactate, propyl lactate or butyl lactate, the other group is methyl, ethyl, vinyl, isopropyl or n-propyl, and the carbon number is C1～C4Alkoxy group, methyl lactateEthyl lactate, propyl lactate or butyl lactate; q is C1～C4An alkoxy group;
a. b and c are positive integers of 1-10.
2. The silicone oligomer for bonding an electrode of a lithium battery according to claim 1, wherein: the values of a, b and c in the formula I satisfy the condition that: a + b + c is more than or equal to 5 and less than or equal to 20.
3. The method for preparing the silicone oligomer for bonding lithium battery electrodes according to claim 1 or 2, characterized in that: which comprises the following steps:
1) sequentially adding alkyl alkoxy silane, fluoro alkyl alkoxy silane and lactate silane into a dosage mixer, adding a diluent which does not react with siloxane and a supported catalyst, and continuously stirring uniformly at room temperature to obtain a silane mixed solution;
2) adding a diluent which does not react with siloxane into metered water to obtain a diluent of water, dropwise adding the silane mixed solution obtained in the step 1) and the diluent of the water into a tubular static reaction mixer at a constant speed at room temperature to realize quantitative, timed and uniform mixing, and after dropwise adding, adding the mixture into a second reactor to obtain a primary hydrolyzed/condensed siloxane oligomer; the mass ratio of the siloxane-unreactive diluent added into the water to the water is 5-10: 1; the molar weight of the added water is the same as the molar equivalent of alkoxy in the silane mixed solution;
3) and heating the second reactor to 40-80 ℃ for further hydrolysis/condensation reflux reaction, filtering out the solid supported catalyst when the equivalent hydrolysis/condensation between the alkoxy and water is finished, and removing the diluent to obtain the lactate-based siloxane oligomer for bonding the lithium battery electrode.
4. The method for preparing the silicone oligomer for bonding electrodes of lithium batteries according to claim 3, wherein: the molecular formula of the alkylalkoxy silane, the fluoro-alkylalkoxy silane or the lactate ester silane is shown as a formula II:
Rn-Si(OR7)(4-n)formula II;
when the formula of formula II represents an alkylalkoxysilane, R is a carbon chain number C3～C16Saturated or unsaturated alkyl, cycloalkyl or aryl; r7Is C1～C4An alkyl group; n is an integer of 1 or 2;
when formula II represents a fluoroalkylalkoxysilane, R is C3～C8Perfluoroalkyl ethyl, perfluoroalkyl methyl, perfluoroalkyl vinyl, perfluoroalkyl isopropyl or perfluoroalkyl n-propyl, R7Is C1～C4Alkyl, n is an integer of 1 or 2;
when the formula of formula II represents lactylsilane, R is carbon chain number C3～C16Saturated or unsaturated alkyl, cycloalkyl or aryl; r7Is methyl lactate, ethyl lactate, propyl lactate or butyl lactate; n is an integer of 1 or 2.
5. The method for preparing the silicone oligomer for bonding lithium battery electrodes as claimed in claim 4, wherein: the alkylalkoxysilane is octyl triethoxysilane, propyl triethoxysilane, hexadecyl trimethoxysilane, dodecyl triethoxysilane, methylpropyl dimethoxysilane, methylpropyl diethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methyloctyl dimethoxysilane, methyloctyl diethoxysilane, methyldodecyl dimethoxysilane, methyldodecyl diethoxysilane, methylhexadecyl dimethoxysilane, and methylhexadecyl diethoxysilane;
the fluoroalkyl alkoxy silane is methyl perfluorooctyl ethyl dimethoxy silane, methyl perfluorooctyl ethyl diethoxy silane, perfluorooctyl ethyl trimethoxy silane, perfluorooctyl ethyl triethoxy silane, methyl perfluorotridecyl ethyl dimethoxy silane, methyl perfluorotridecyl ethyl diethoxy silane, perfluorotridecyl ethyl trimethoxy silane or perfluorotridecyl ethyl triethoxy silane;
the lactate silane is vinyl methyl trilactate silane, vinyl propyl trilactate silane, vinyl butyl trilactate silane, vinyl ethyl trilactate silane, methyl vinyl ethyl dilactate silane and dimethyl ethyl dilactate silane.
6. The method for preparing the silicone oligomer for bonding electrodes of lithium batteries according to claim 3, wherein: the diluent which does not react with siloxane is one or a mixture of more than two of the following: methanol, ethanol, isopropanol, n-propanol, tetrahydrofuran, acetone, butanone, ethyl acetate or butyl acetate.
7. The method for preparing the silicone oligomer for bonding electrodes of lithium batteries according to claim 3, wherein: the carrier used by the supported catalyst is one or a mixture of more than two of the following components: clay, styrene type spherical exchange resin, porous silica gel, precipitated or fumed silica, porous alumina, aluminum silicate, or porous ceramic.
8. The method for preparing the silicone oligomer for bonding electrodes of lithium batteries according to claim 3, wherein: the catalyst is an acid type catalyst, and the acid type catalyst is one of the following: titanate type, sulfuric acid type, phosphoric acid type, or sulfonic acid group type.
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| US2758127A (en) * | 1953-12-30 | 1956-08-07 | California Research Corp | Method of preparing silicon esters by reacting an alkoxysilanol with an alkoxysilamine |
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| US9160003B2 (en) * | 2010-12-21 | 2015-10-13 | Uchicago Argonne, Llc | Polysiloxane binder for lithium ion battery electrodes |
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